CN104035278A - Photosensitive Resin Composition And Spacer Preprared From The Same - Google Patents

Photosensitive Resin Composition And Spacer Preprared From The Same Download PDF

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Publication number
CN104035278A
CN104035278A CN201410086476.1A CN201410086476A CN104035278A CN 104035278 A CN104035278 A CN 104035278A CN 201410086476 A CN201410086476 A CN 201410086476A CN 104035278 A CN104035278 A CN 104035278A
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CN
China
Prior art keywords
phenyl
methyl
dimethylamino
butanone
morpholino phenyl
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Pending
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CN201410086476.1A
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Chinese (zh)
Inventor
赵庸桓
井上胜治
张元凡
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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Publication of CN104035278A publication Critical patent/CN104035278A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Abstract

The present invention relates to a photosensitive resin composition and a spacer prepared from the same. In specific, the photosensitive resin composition includes an alkali-soluble resin, a photocurable monomer, a photopolymerization initiator, an amino acetophenone-based or amino benzaldehyde acetophenone-based hydrogen donor, and a solvent, thereby improving photoreactivity by activating alkyl radicals generated from the photopolymerization initiator and providing improved sensitivity by maximizing light efficiency. Accordingly, the sensitivity of the photosensitive resin composition is largely improved.

Description

Photosensitive polymer combination and the sept that uses said composition to manufacture
Technical field
The sept that the present invention relates to a kind of photosensitive polymer combination and use said composition to manufacture, more specifically, relates to a kind of the have photosensitive polymer combination of high sensitivity and high crosslink density and the sept that uses said composition to manufacture.
Background technology
General display device is constant in order to maintain interval between upper and lower base plate, and uses silica bead or the plastic bead etc. with certain diameter.But, in the time that it is positioned at pixel inside, there is the problem of aperture opening ratio (aperture ratio) decline and generation light leak in above-mentioned bead random dispersion on substrate.In order to solve such problem, use in the inside of display device the sept being formed by photoetching process, in recent years, in the manufacture of the sept for image display device, adopted photoetching process to become general technology.
The method that is formed sept by photoetching process refers to, photosensitive resin coating composition on substrate, and via mask irradiation ultraviolet radiation, and by developing process, the desired position on substrate forms sept with being formed at that pattern on mask is identical afterwards.
But, in order to prevent the pollution of be coated with photosensitive polymer combination and mask, just need to make mask and the substrate that is coated with photosensitive polymer combination maintain certain interval.But, be diffused into above-mentioned interval owing to having passed through the light of mask, therefore there is the exposure problem wider than the size in the design of mask pattern.
In recent years, in order to improve the sharpness of picture quality, and make the size decreases of pixel, and also required sept to have the fine pattern that size is little thereupon, therefore people's strong request addresses the above problem.
In order to address the above problem, Korea S's publication 10-2001-0100808 communique and 10-2002-0053757 communique disclose the technology that forms the sept of point-like or strip by following method, but this technology can not address the above problem, described method refers to, use polymer adhesive as acrylic copolymer, the photosensitive polymer combination that coating is made up of multicomponent methacrylate crosslinking chemical and Photoepolymerizationinitiater initiater on substrate, afterwards via the mask irradiation ultraviolet radiation specifying, and make desired partly solidified, and uncured part is washed with aqueous alkali and the method removed.
Prior art document
Patent documentation
Patent documentation 1: Korea S publication 10-2001-0100808 communique
Patent documentation 2: Korea S publication 10-2002-0053757 communique
Summary of the invention
Invent problem to be solved
The object of the invention is to, even if provide a kind of due to highly sensitive, therefore also high photosensitive polymer combination of cross-linking density under low exposure.
In addition, the object of the present invention is to provide a kind of following photosensitive polymer combination: the adaptation excellence of this photosensitive polymer combination and substrate, in developing procedure, can there is not coming off of pattern, and can form and there is excellent elastic recovery rate and T/B ratio, there is the sept that causes the less rigid characteristic of distortion because of external pressure simultaneously.
Another object of the present invention is to, provide a kind of above-mentioned photosensitive polymer combination is coated with into the pattern of regulation the sept that makes it to be solidified to form.
Another object of the present invention is, a kind of image display device that comprises above-mentioned sept is provided.
For solving the method for problem
1. a photosensitive polymer combination, comprises alkali soluble resin, photo-curable monomer, Photoepolymerizationinitiater initiater, aminoacetophenone class or amino benzaldehyde hydrogen donor and solvent.
2. according to the photosensitive polymer combination described in above-mentioned project 1, wherein, above-mentioned aminoacetophenone class or amino benzaldehyde hydrogen donor are the compounds shown in following Chemical formula 1.
[chemistry 1]
(in above formula, R 1and R 2independent is respectively the alkyl of the straight or branched of carbon number 1～6, R 3that hydrogen, hydroxyl or carbon number are the alkyl of 1～10 straight or branched.〕
3. according to the photosensitive polymer combination described in above-mentioned project 1, wherein, described aminoacetophenone class hydrogen donor is to dimethylamino acetophenone.
4. according to the photosensitive polymer combination described in above-mentioned project 1, wherein, with respect to the composition of 100 weight portions, the described aminoacetophenone class or the amino benzaldehyde hydrogen donor that contain 0.1～20 weight portion.
5. according to the photosensitive polymer combination described in above-mentioned project 1, wherein, described Photoepolymerizationinitiater initiater comprises at least one Photoepolymerizationinitiater initiater being selected from acetophenones, bisglyoxaline class and oximes.
6. according to the photosensitive polymer combination described in above-mentioned project 5, wherein, described acetophenones Photoepolymerizationinitiater initiater is to be selected from diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzil dimethyl ketal, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-(2-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-Ethylbenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-propyl group benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-butyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2,3-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2,4-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methyl-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(the bromo-4-methoxy-benzyl of 2-)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer of propane-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-propyl group-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-butyl-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) propane-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) butane-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) propane-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) butane-1-ketone, 2-methyl-2-methylamino (4-morpholino phenyl) propane-1-ketone, 2-methyl-2-dimethylamino (4-morpholino phenyl) propane-1-ketone, at least one in 2-methyl-2-diethylamino (4-morpholino phenyl) propane-1-ketone.
7. according to the photosensitive polymer combination described in above-mentioned project 5, wherein, described bisglyoxaline class Photoepolymerizationinitiater initiater is to be selected from 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2, 3-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(alkoxyl phenyl) bisglyoxaline, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(dialkoxy phenyl) bisglyoxaline, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(tri-alkoxy phenyl) bisglyoxalines and 4, 4 ', 5, at least one in the imidazolium compounds that the phenyl of 5 ' is replaced by alkoxy carbonyl group.
8. according to the photosensitive polymer combination described in above-mentioned project 5, wherein, described oximes Photoepolymerizationinitiater initiater is to be selected from least one in compound shown in compound shown in O-carbethoxyl group-α-oximido-1-phenyl-propane-1-ketone, following chemical formula 5 and following chemical formula 6.
[chemistry 2]
[chemistry 3]
9. a sept, described sept is to be formed by the photosensitive polymer combination described in any one in above-mentioned project 1 to 8.
10. an image display device, it comprises the sept described in above-mentioned project 9.
Invention effect
Photosensitive polymer combination of the present invention, by comprising aminoacetophenone class or amino benzaldehyde hydrogen donor, thereby activate the alkyl diradical being produced by Photoepolymerizationinitiater initiater, and further make photoreactivity improve, optical efficiency reaches to greatest extent, therefore has the sensitivity after significantly improving.By the raising of above-mentioned sensitivity, though when curing with little exposure, also there is enough cross-linking densities, and can shorten the time shutter.
In addition, because photosensitive polymer combination of the present invention is in the adaptation excellence of solidifying rear and substrate, therefore coming off of pattern can not occur in developing procedure, the shape maintains performance of pattern is also excellent.
In addition, the sept of being manufactured by photosensitive polymer combination of the present invention, has excellent elastic recovery rate and T/B ratio, and has and cause the less rigid characteristic of distortion because of external pressure.
In addition, if and with photosensitive polymer combination of the present invention and oxime ester class Photoepolymerizationinitiater initiater, because sensitivity becomes well, and further improved adaptation and the pattern Formation and characteristics when curing, therefore solvent resistance and thermotolerance all improve, and transparency also uprises.
Brief description of the drawings
Fig. 1 is the schematic diagram that represents the definition of T/B ratio.
Embodiment
The invention provides a kind of following photosensitive polymer combination: this photosensitive polymer combination comprises alkali soluble resin, photo-curable monomer, Photoepolymerizationinitiater initiater, aminoacetophenone class or amino benzaldehyde hydrogen donor and solvent, thereby activate the alkyl diradical being produced by Photoepolymerizationinitiater initiater, and further make photoreactivity improve, optical efficiency reaches to greatest extent, and therefore this photosensitive polymer combination has the sensitivity after significantly improving.
The present invention is described in further detail below.
< aminoacetophenone class or amino benzaldehyde hydrogen donor >
Photosensitive polymer combination of the present invention comprises aminoacetophenone class or amino benzaldehyde hydrogen donor.
Aminoacetophenone class or amino benzaldehyde hydrogen donor, can activate the alkyl diradical being produced by Photoepolymerizationinitiater initiater in the time of irradiation, and further make photoreactivity improve, and optical efficiency reaches to greatest extent, and therefore the sensitivity of photosensitive polymer combination is improved.In this respect, owing to supplying with hydrogen from aminoacetophenone class or amino benzaldehyde hydrogen donor to the α position of nitrogen-atoms, therefore in order further to supply with hydrogen, and preferred nitrogen atom is replaced by alkyl.
About the example more specifically of aminoacetophenone class of the present invention or amino benzaldehyde hydrogen donor, as shown in following Chemical formula 1.
[chemistry 4]
(in above formula, R 1and R 2independent is respectively the alkyl of the straight or branched of carbon number 1～6, R 3that hydrogen, hydroxyl or carbon number are the alkyl of 1～10 straight or branched, preferably R 3that hydrogen or carbon number are the alkyl of 1～10 straight or branched, more preferably R 3hydrogen.〕
The preferred example of aminoacetophenone class hydrogen donor of the present invention is, to dimethylamino acetophenone.
The content of aminoacetophenone class of the present invention and amino benzaldehyde hydrogen donor, can suitably regulate as required, for example, with respect to the photosensitive polymer combination of 100 weight portions, the content of above-mentioned hydrogen donor is 0.1～20 weight portion, this can not reduce other physicochemical property owing to making the sensitivity of photosensitive polymer combination improve, the therefore content of preferred above-mentioned hydrogen donor, but be not limited in this.
Photosensitive polymer combination of the present invention, except comprising aminoacetophenone class and amino benzaldehyde hydrogen donor, can also comprise being not particularly limited for the composition of photosensitive polymer combination in this area.For example, can also further comprise alkali soluble resin, photo-curable monomer, Photoepolymerizationinitiater initiater, solvent etc.
< alkali soluble resin >
Conventionally, alkali soluble resin has reactive and alkali dissolubility because of the effect of light or heat, and plays the effect as the dispersion medium of other compositions.The alkali soluble resin that photosensitive polymer combination of the present invention is contained, preferably be prepared by comprising the monomer with epoxy radicals tristane ring structure and unsaturated link, more than more preferably above-mentioned monomer comprises at least one in the monomer shown in following Chemical formula 2 and chemical formula 3.
[chemistry 5]
(in above formula, R 1hydrogen or to comprise or do not comprise heteroatomic carbon number be 1～20 alkyl or cycloalkyl, R 2it is singly-bound or to comprise or do not comprise heteroatomic carbon number be 1～20 alkylidene or ring alkylidene, above-mentioned R 1and R 2can independently be replaced by hydroxyl respectively.〕
[chemistry 6]
(in above formula, R 1hydrogen or to comprise or do not comprise heteroatomic carbon number be 1～20 alkyl or cycloalkyl, R 2it is singly-bound or to comprise or do not comprise heteroatomic carbon number be 1～20 alkylidene or ring alkylidene, above-mentioned R 1and R 2can independently be replaced by hydroxyl respectively.〕
In above-mentioned Chemical formula 2 and chemical formula 3, as R 1example more specifically, list independently respectively: hydrogen; The alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group; The alkyl that methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyl-n-pro-pyl, 2-hydroxyl-n-pro-pyl, 3-hydroxyl-n-pro-pyl, 1-hydroxyl-isopropyl, 2-hydroxyl-isopropyl, 1-hydroxyl-normal-butyl, 2-hydroxyl-normal-butyl, 3-hydroxyl-normal-butyl, 4-hydroxyl-normal-butyl etc. contain hydroxyl.Wherein, be preferably R 1respectively independent is hydrogen, methyl, methylol, 1-hydroxyethyl or 2-hydroxyethyl, particularly more preferably hydrogen or methyl.
In above-mentioned Chemical formula 2 and chemical formula 3, as R 2example more specifically, list independently respectively: singly-bound; The alkylidenes such as methylene, ethylidene, propylidene; Oxidation methylene, oxyethylene group, oxypropylene group, methylene sulfenyl (thiomethylene), sub-ethylmercapto group (thioethylene), sub-rosickyite base (thiopropylene), aminomethylene, amino ethylidene, Aminopropylidene etc. contain heteroatomic alkylidene.Wherein, be preferably R 2singly-bound, methylene, ethylidene, oxidation methylene or oxyethylene group, particularly R more preferably 2singly-bound or oxyethylene group.In the present invention, work as R 2during for singly-bound, mean 8 or the carbon of 9 and the acrylate-based direct combination of oxygen of three ring decyls.
As the example more specifically of such monomer with epoxy radicals tristane ring structure and unsaturated link, can enumerate: epoxy radicals two is encircled decyl (methyl) acrylate-3 4-epoxy radicals tristane-9-base (methyl) acrylate; 3,4-epoxy radicals tristane-9-base (methyl) acrylate; Epoxy radicals two is encircled decyl (methyl) acrylate-3,4-epoxy radicals tristane-8-base (methyl) acrylate; 3,4-epoxy radicals tristane-8-base (methyl) acrylate; Epoxy radicals two cyclopentyl ethoxy (methyl) acrylate-2-(3,4-epoxy radicals tristane-9-base oxygen base) ethyl (methyl) acrylate; Epoxy radicals two cyclopentyl ethoxy (methyl) acrylate-2-(3,4-epoxy radicals tristane-8-base oxygen base) ethyl (methyl) acrylate; Epoxy radicals two cyclopentyloxy hexyl (methyl) acrylate; Epoxy radicals two is encircled decyl (methyl) acrylate etc., preferably lists epoxy radicals two and encircles decyl (methyl) acrylate, epoxy radicals two cyclopentyl ethoxy (methyl) acrylate etc.These compositions can use separately respectively or be used in combination two or more.
In the present invention, (methyl) acrylate refers to acrylate and/or methacrylate.
Alkali soluble resin of the present invention, carries out copolymerization at interior monomer and prepares comprising the monomer with above-mentioned epoxy radicals tristane ring structure and unsaturated link.More specifically, can by following (a) monomer, (b) monomer and (c) monomer carry out copolymerization and prepare, described (a) monomer has epoxy radicals tristane ring structure and unsaturated link; Described (b) monomer can carry out copolymerization with the monomer with above-mentioned epoxy radicals tristane ring structure and unsaturated link; Described (c) monomer has the unsaturated link forming with carboxyl.
As the object lesson of above-mentioned (b) monomer, can enumerate following monomer.
First, can enumerate: styrene, chlorostyrene, vinyltoluene, α-methyl styrene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to aromatic vinyl base class monomers such as vinyl benzyl glycidol ether, indenes, wherein, vinyltoluene because of its developability and manufacturability preferably excellent.Can also enumerate: N-N-cyclohexylmaleimide, N-benzyl maleimide, N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, hydroxy phenyl maleimide between N-, N-p-hydroxybenzene maleimide, N-o-methyl-phenyl-maleimide, aminomethyl phenyl maleimide between N-, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, the N-substituted maleimide monomers such as N-p-methoxyphenyl maleimide, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) benzyl acrylate, (methyl) dimethylaminoethyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-phenoxy ethyl, (methyl) tetrahydrofurfuryl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) 2-hydroxy-3-chloropropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, acyl group octyloxy-2-hydroxypropyl (methyl) acrylate, EHA, (methyl) acrylic acid-2-methoxyl ethyl ester, (methyl) acrylic acid-3-methoxyl butyl ester, ethoxydiglycol (methyl) acrylate, methoxyl triethylene glycol (methyl) acrylate, methoxyl tripropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group diglycol (methyl) acrylate, to Nonylphenoxy polyglycol (methyl) acrylate, to Nonylphenoxy polypropylene glycol (methyl) acrylate, (methyl) acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid-1,1,1,3,3,3-hexafluoro isopropyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid 17 fluorine esters in the last of the ten Heavenly stems, (methyl) tribromophenyl acrylate, β-(methyl) acyloxy ethyl hydrogen succinate ester, acrylic acid methyl-α-hydroxyl methyl esters, acrylic acid ethyl-α-hydroxyl methyl esters, acrylic acid propyl group-α-hydroxyl methyl esters, (methyl) acrylic ester monomer of acrylic acid butyl-α-hydroxyl methyl esters etc., acrylic acid-2-amino ethyl ester, methacrylic acid-2-amino ethyl ester, acrylic acid-2-dimethylaminoethyl, methacrylic acid-2-dimethylaminoethyl, the amino propyl ester of acrylic acid-2-, the amino propyl ester of methacrylic acid-2-, acrylic acid-2-dimethylamino propyl ester, methacrylic acid-2-dimethylamino propyl ester, the amino propyl ester of acrylic acid-3-, the amino propyl ester of methacrylic acid-3-, acrylic acid-3-dimethylamino propyl ester, the unsaturated carboxylic acid aminoalkyl esters monomers such as methacrylic acid-3-dimethylamino propyl ester, the generating vinyl carboxylate esters monomers such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate, the unsaturated ethers such as methoxy ethylene, ethyl vinyl ether, allyl glycidyl ether, the vinyl cyanide base class monomers such as vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile, the sub-ethene of two cyanogen, the unsaturated acyl amines such as acrylamide, Methacrylamide, α-chloropropene acid amides, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide, the aliphatics conjugated diene monomers such as 1,3-butadiene, isoprene, chlorbutadiene, and there is macromonomer of single acryloyl group or monomethyl acryloyl group etc. at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethylmethacrylate, the positive butyl ester of polyacrylic acid, Vinalac 5920, polysiloxane.These monomers can use separately respectively or be used in combination two or more.
As above-mentioned (c) monomer with the unsaturated link forming with carboxyl, as long as having the carboxylic acid compound of polymerisable unsaturated double-bond, there is no particular limitation as to it, particularly, for example, can enumerate acrylic acid, methacrylic acid etc.Acrylic acid, methacrylic acid can use separately respectively or be used in combination two or more.In addition, can also be in these acrylic or methacrylic acid, use after adding more than one other acid again.As other acid, can use unsaturated monocarboxylic acid or unsaturated polybasic carboxylic acid, particularly, can also and use more than one the carboxylic acid of selecting from other the unsaturated carboxylic acid such as crotonic acid, itaconic acid, mesaconic acid, citraconic acid, maleic acid, fumaric acid.In addition, the monomer with the unsaturated link forming with carboxyl refers to acid anhydrides, and above-mentioned unsaturated polybasic acid anhydride for example can be enumerated maleic anhydride, itaconic anhydride, citraconic anhydride etc.
In addition, list (the 2-methacryloxy alkyl) ester that above-mentioned unsaturated polybasic carboxylic acid is this unsaturated polybasic carboxylic acid, for example, can enumerate: mono succinate (2-acryloxy ethyl) ester, mono succinate (2-methacryloxyethyl) ester, phthalic acid list (2-acryloxy ethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc.
Above-mentioned unsaturated polybasic carboxylic acid refers to, list (methyl) acrylate of the dicarboxyl polymkeric substance of two ends of this unsaturated polybasic carboxylic acid, for example, can enumerate: ω-carboxyl polycaprolactone single-acrylate, ω-carboxyl polycaprolactone monomethacrylates etc.
In addition, above-mentioned unsaturated polybasic carboxylic acid refers to, comprises the unsaturated acrylate of hydroxyl and carboxyl in same a part, for example, can enumerate α-(methylol) acrylic acid etc.
Wherein, acrylic acid, methacrylic acid, maleic anhydride etc. are because of the high preferably use of reactivity of copolymerization.
According to the present invention, in the multipolymer (the present invention also comprises: the situation that the monomer further comprising except a～c is carried out to copolymerization) that above-mentioned (a)～(c) is carried out to copolymerization and obtain, about by (a)～(c) ratio of derivative constituent respectively, with respect to the total mole number of constituent that forms above-mentioned multipolymer, be preferably following scope in mole fraction.
By (a) derivative structural unit: 2～50 % by mole
By (b) derivative structural unit: 2～50 % by mole
By (c) derivative structural unit: 2～70 % by mole
As mentioned above, if by (a)～(c) ratio of derivative constituent, in above-mentioned scope,, due to developability, solubility and stable on heating balance excellence, therefore can obtain preferred multipolymer respectively.
According to one embodiment of present invention, about alkali soluble resin, by in the multipolymer that above-mentioned (a)～(c) copolyreaction of monomer obtains, add (d) in a molecule, to there is the compound of unsaturated link and epoxy radicals, can give light/Thermocurable to alkali soluble resin thus.
In a molecule, there is the object lesson of the compound of unsaturated link and epoxy radicals as above-mentioned (d), can enumerate (methyl) glycidyl acrylate, (methyl) acrylic acid-3,4-epoxy cyclohexyl, (methyl) acrylic acid-3,4-epoxycyclohexyl methyl esters, (methyl) acrylic acid methyl ethylene oxidic ester etc.Wherein, preferably use (methyl) glycidyl acrylate.These compositions can use separately respectively or be used in combination two or more.In the present invention, (methyl) acrylate refers to acrylate and/or (methyl) acrylate.
With respect to thering is the molal quantity of the constituent of the compound deriving of carboxyl and unsaturated link by (c) in above-mentioned multipolymer, in mole fraction, the compound that above-mentioned (d) has unsaturated link and epoxy radicals in a molecule preferably reacts with 5～80 % by mole, more preferably 10～70 % by mole.If (d) have the compound of unsaturated link and epoxy radicals in above-mentioned numerical range, owing to can obtaining sufficient photo-curable or Thermocurable, sensitivity and pencil hardness all become well, and reliability excellence is therefore preferred.
Alkali soluble resin of the present invention can adopt method well known in the art to be prepared, in known polymerization, and more preferably solution polymerization process.In addition, polymerization temperature and polymerization time be according to the kind of monomer importing and ratio, target adhesive resin molecular weight and acid number and difference, but preferably polymerization 1～10 hour at 60 DEG C～130 DEG C.
For the solvent of above-mentioned operation, the solvent using can use common Raolical polymerizable time, specifically can enumerate tetrahydrofuran, dioxan, glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethylhexoate, acetic acid-3-methoxyl butyl ester, methyl alcohol, ethanol, propyl alcohol, normal butyl alcohol, glycol monoethyl ether, propylene glycol monomethyl ether, toluene, dimethylbenzene, ethylbenzene, chloroform, dimethyl sulfoxide etc.These solvents can use separately or be used in combination two or more.
In addition, as the polymerization initiator for above-mentioned operation, can add normally used polymerization initiator, there is no particular limitation as to it.Specifically can enumerate: the organic peroxides such as di-isopropylbenzene hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, tert-butylperoxy isopropyl carbonate, peroxidating 2 ethyl hexanoic acid tert-pentyl ester, the peroxidating 2-ethylhexyl carbonic acid tert-butyl ester; 2,2 '-azo two (isobutyronotrile), 2,2 '-azo two (2,4-methyl pentane nitrile), dimethyl 2, the nitrogen compounds such as 2 '-azo two (2 Methylpropionic acid ester).These compositions can use separately or be used in combination two or more.
In addition, in order to control molecular weight or molecular weight distribution in polymerization process, above-mentioned multipolymer can also use the chain-transferring agents such as sulfydryl class chain-transferring agent, α-methyl styrene dimer such as n-dodecyl mercaptan, mercaptoacetic acid, methyl thioglycolate.With respect to the total amount of monomer, the use amount of above-mentioned α-methyl styrene dimer or sulfhydryl compound counts 0.005～5% with quality criteria.In addition, about above-mentioned polymerizing condition, the thermal value etc. of considering manufacturing equipment and producing because of polymerization, can also suitably regulate feeding method and temperature of reaction.
In the present invention, the acid number of alkali soluble resin is in the preferred scope at 20～200mgKOH/g of pressed powder benchmark.If acid number, in above-mentioned scope, can have excellent elastic recovery rate after solidifying.
The weight-average molecular weight with polystyrene conversion of alkali soluble resin, preferably in 3000～100000 scope, more preferably in 5000～50000 scope.If the weight-average molecular weight of alkali soluble resin, in 3000～100000 scope, reduces owing to being difficult to occur film in the time developing, the deciduous of non-pixel portion when development is good, therefore preferred.
The molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] of alkali soluble resin is preferably 1.5～6.0, and more preferably 1.8～4.0.If molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is 1.5～6.0, due to developability excellence, therefore preferred.
With respect to all pressed powders of composition, the content of alkali soluble resin is preferably 5～90 quality % in mass fraction, more preferably 20～70 quality %.If in above-mentioned scope, owing to can not remain residue in the time developing, and can form desired film, therefore preferred.
< photo-curable monomer >
Photo-curable monomer is the compound that effect by light and above-mentioned Photoepolymerizationinitiater initiater can polymerization, can enumerate monofunctional monomer, two functional monomers, other polyfunctional monomer etc.
In order to improve developability, sensitivity, adaptation, the problem on surface etc. of photosensitive polymer combination, for photo-curable monomer of the present invention, can mix the photo-curable monomer that uses the structure of functional group or different two or more of number of functional groups, and its scope is not limited.
As the object lesson of monofunctional monomer, can enumerate nonyl phenyl carbitol acrylate, 2-hydroxyl-3-phenoxy propyl acrylate, 2-ethylhexyl carbitol acrylate, acrylic acid-2-hydroxyl ethyl ester, NVP etc.
As two functional monomers' object lesson, can enumerate two (acrylyl oxy-ethyl) ethers, 3-methyl pentanediol two (methyl) acrylate etc. of 1,6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, two (methyl) acrylic acid DOPCP, triethylene glycol two (methyl) acrylate, bisphenol-A.
As other the object lesson of polyfunctional monomer, can enumerate trimethylolpropane tris (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, ethoxylation dipentaerythritol six (methyl) acrylate, propoxylation dipentaerythritol six (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.
Wherein, preferably use polyfunctional monomers more than two senses.
In mass fraction, photo-curable monomer is generally 1～60 quality % with respect to the pressed powder in photosensitive polymer combination, preferably in the scope of 5～50 quality %, uses photo-curable monomer.In said reference, if photo-curable monomer is in the scope of 1～60 quality %, due to intensity and the flatness excellence of pixel portion, therefore preferred.
< Photoepolymerizationinitiater initiater >
Photosensitive polymer combination of the present invention, can use Photoepolymerizationinitiater initiater used in the art and be not particularly limited.
For example, can be used singly or in combination respectively two or more following compounds: i.e. acetophenone compounds, bisglyoxaline compounds, oxime compound, compound in triazine class, acylphosphine oxide compounds, benzoin compounds, benzophenone compound, thioxanthones compounds, anthracene compounds etc.
As above-mentioned acetophenone compounds, for example, can enumerate: diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzil dimethyl ketal, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-(2-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-Ethylbenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-propyl group benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-butyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2,3-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2,4-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methyl-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(the bromo-4-methoxy-benzyl of 2-)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer etc. of propane-1-ketone.
In addition, as the acetophenone compounds that can also use, for example, can enumerate the compound shown in following chemical formula 4 except the acetophenone compounds of above-mentioned example.
[chemistry 7]
(in above formula, R 1～R 4the naphthyl that the benzyl that the independent phenyl replacing for hydrogen atom, halogen atom, hydroxyl, the alkyl that can is 1～12 by carbon number, the alkyl that can is 1～12 by carbon number replace respectively or the alkyl that can be 1～12 by carbon number replace.〕
As the object lesson of the compound shown in above-mentioned chemical formula 4, can enumerate 2-methyl-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-propyl group-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-butyl-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) propane-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) butane-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) propane-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) butane-1-ketone, 2-methyl-2-methylamino (4-morpholino phenyl) propane-1-ketone, 2-methyl-2-dimethylamino (4-morpholino phenyl) propane-1-ketone, 2-methyl-2-diethylamino (4-morpholino phenyl) propane-1-ketone etc.
As above-mentioned united imidazole, for example can enumerate 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2, 3-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(alkoxyl phenyl) bisglyoxaline, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(dialkoxy phenyl) bisglyoxaline, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(tri-alkoxy phenyl) bisglyoxalines or 4, 4 ', 5, the imidazolium compounds that the phenyl of 5 ' is replaced by alkoxy carbonyl group etc.Wherein, preferably use 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline or 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.
As above-mentioned oxime compound, can be used singly or in combination respectively two or more following compounds: i.e. compound shown in compound and following chemical formula 6 shown in O-carbethoxyl group-α-oximido-1-phenyl-propane-1-ketone, following chemical formula 5 etc.
[chemistry 8]
[chemistry 9]
As above-mentioned compound in triazine class, for example can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-of 4-piperonyl-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl of 4-]-1, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl of 4-]-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.
As above-mentioned acylphosphine oxide compounds, for example, can enumerate TMDPO etc.
As above-mentioned benzoin compounds, for example, can enumerate benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether etc.
As above-mentioned benzophenone compound; for example can enumerate benzophenone, O-benzoyl methyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3; 3 '; 4; 4 '-tetra-(t-butyl peroxy carbonyl) benzophenone, 2; 4,6-tri-methyl benzophenone etc.
As above-mentioned thioxanthones compounds, for example, can enumerate ITX, 2,4-diethyl thioxanthene
[chemistry 11]
[chemistry 12]
[chemistry 13]
[chemistry 14]
[chemistry 15]
In addition, can make to use up and/or hot cationic polymerization initiators.
Light and/or hot cationic polymerization initiators, can also use the polymerization initiator forming by kation with from lewis acidic negative ion.
As above-mentioned cationic object lesson, can enumerate diphenyl iodine, two (p-methylphenyl) iodine, two (to tert-butyl-phenyl) iodine, two (to octyl phenyl) iodine, two (to octadecyl phenyl) iodine, two (to octyloxyphenyl) iodine, two (to octadecane oxygen base phenyl) iodine, phenyl (to octadecane oxygen base phenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, triphenylsulfonium, three (p-methylphenyl) sulfonium, three (p-isopropyl phenyl) sulfonium, three (2,6-3,5-dimethylphenyl) sulfonium, three (to tert-butyl-phenyl) sulfonium, three (to cyano-phenyl) sulfonium, three (rubigan) sulfonium, dimethyl (methoxyl) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxyl group) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecane oxygen base) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluorine methoxyl) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromine propoxyl group) sulfonium, dimethyl (4-cyano group butoxy) sulfonium, dimethyl (8-nitro octyloxy) sulfonium, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, dimethyl (2-hydroxyl isopropoxy) sulfonium, or dimethyl (three (trichloromethyl) methyl) sulfonium etc.
As preferred kation, can enumerate two (p-methylphenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to tert-butyl-phenyl) iodine, triphenylsulfonium or three (to tert-butyl-phenyl) sulfonium etc.As the above-mentioned object lesson from lewis acidic negative ion, can enumerate hexafluorophosphate, hexafluoro arsenate, hexafluoro antimonate or four (pentafluorophenyl group) borate etc.As the preferred object lesson from lewis acidic negative ion, can enumerate hexafluoro antimonate or four (pentafluorophenyl group) borate etc.
Above-mentioned kation and can combination in any from lewis acidic negative ion.
As the object lesson of cationic polymerization initiators, can enumerate diphenyl iodine hexafluorophosphate, two (p-methylphenyl) iodine hexafluorophosphate, two (to tert-butyl-phenyl) iodine hexafluorophosphate, two (to octyl phenyl) iodine hexafluorophosphate, two (to octadecyl phenyl) iodine hexafluorophosphate, two (to octyloxyphenyl) iodine hexafluorophosphate, two (to octadecane oxygen base phenyl) iodine hexafluorophosphate, phenyl (to octadecane oxygen base phenyl) iodine hexafluorophosphate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluorophosphate, methyl naphthalene iodide hexafluorophosphate, ethyl naphthalene iodide hexafluorophosphate, triphenylsulfonium hexafluorophosphate, three (p-methylphenyl) sulfonium hexafluorophosphate, three (p-isopropyl phenyl) sulfonium hexafluorophosphate, three (2,6-3,5-dimethylphenyl) sulfonium hexafluorophosphate, three (to tert-butyl-phenyl) sulfonium hexafluorophosphate, three (to cyano-phenyl) sulfonium hexafluorophosphate, three (rubigan) sulfonium hexafluorophosphate, dimethyl naphthyl sulfonium hexafluorophosphate, diethyl naphthyl sulfonium hexafluorophosphate, dimethyl (methoxyl) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxyl group) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octadecane oxygen base) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluorine methoxyl) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromine propoxyl group) sulfonium hexafluorophosphate, dimethyl (4-cyano group butoxy) sulfonium hexafluorophosphate, dimethyl (8-nitro octyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluorophosphate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluorophosphate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluorophosphate, diphenyl iodine hexafluoro arsenate, two (p-methylphenyl) iodine hexafluoro arsenate, two (to tert-butyl-phenyl) iodine hexafluoro arsenate, two (to octyl phenyl) iodine hexafluoro arsenate, two (to octadecyl phenyl) iodine hexafluoro arsenate, two (to octyloxyphenyl) iodine hexafluoro arsenate, two (to octadecane oxygen base phenyl) iodine hexafluoro arsenate, phenyl (to octadecane oxygen base phenyl) iodine hexafluoro arsenate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro arsenate, methyl naphthalene iodide hexafluoro arsenate, ethyl naphthalene iodide hexafluoro arsenate, triphenylsulfonium hexafluoro arsenate, three (p-methylphenyl) sulfonium hexafluoro arsenate, three (p-isopropyl phenyl) sulfonium hexafluoro arsenate, three (2,6-3,5-dimethylphenyl) sulfonium hexafluoro arsenate, three (to tert-butyl-phenyl) sulfonium hexafluoro arsenate, three (to cyano-phenyl) sulfonium hexafluoro arsenate, three (rubigan) sulfonium hexafluoro arsenate, dimethyl naphthyl sulfonium hexafluoro arsenate, diethyl naphthyl sulfonium hexafluoro arsenate, dimethyl (methoxyl) sulfonium hexafluoro arsenate, dimethyl (ethoxy) sulfonium hexafluoro arsenate, dimethyl (propoxyl group) sulfonium hexafluoro arsenate, dimethyl (butoxy) sulfonium hexafluoro arsenate, dimethyl (octyloxy) sulfonium hexafluoro arsenate, dimethyl (octadecane oxygen base) sulfonium hexafluoro arsenate, dimethyl (isopropoxy) sulfonium hexafluoro arsenate, dimethyl (tert-butoxy) sulfonium hexafluoro arsenate, dimethyl (cyclopentyloxy) sulfonium hexafluoro arsenate, dimethyl (cyclohexyloxy) sulfonium hexafluoro arsenate, dimethyl (fluorine methoxyl) sulfonium hexafluoro arsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoro arsenate, dimethyl (3-bromine propoxyl group) sulfonium hexafluoro arsenate, dimethyl (4-cyano group butoxy) sulfonium hexafluoro arsenate, dimethyl (8-nitro octyloxy) sulfonium hexafluoro arsenate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluoro arsenate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluoro arsenate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluoro arsenate, diphenyl iodine hexafluoro antimonate, two (p-methylphenyl) iodine hexafluoro antimonate, two (to tert-butyl-phenyl) iodine hexafluoro antimonate, two (to octyl phenyl) iodine hexafluoro antimonate, two (to octadecyl phenyl) iodine hexafluoro antimonate, two (to octyloxyphenyl) iodine hexafluoro antimonate, two (to octadecane oxygen base phenyl) iodine hexafluoro antimonate, phenyl (to octadecane oxygen base phenyl) iodine hexafluoro antimonate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro antimonate, methyl naphthalene iodide hexafluoro antimonate, ethyl naphthalene iodide hexafluoro antimonate, triphenylsulfonium hexafluoro antimonate, three (p-methylphenyl) sulfonium hexafluoro antimonate, three (p-isopropyl phenyl) sulfonium hexafluoro antimonate, three (2,6-3,5-dimethylphenyl) sulfonium hexafluoro antimonate, three (to tert-butyl-phenyl) sulfonium hexafluoro antimonate, three (to cyano-phenyl) sulfonium hexafluoro antimonate, three (rubigan) sulfonium hexafluoro antimonate, dimethyl naphthyl sulfonium hexafluoro antimonate, diethyl naphthyl sulfonium hexafluoro antimonate, dimethyl (methoxyl) sulfonium hexafluoro antimonate, dimethyl (ethoxy) sulfonium hexafluoro antimonate, dimethyl (propoxyl group) sulfonium hexafluoro antimonate, dimethyl (butoxy) sulfonium hexafluoro antimonate, dimethyl (octyloxy) sulfonium hexafluoro antimonate, dimethyl (octadecane oxygen base) sulfonium hexafluoro antimonate, dimethyl (isopropoxy) sulfonium hexafluoro antimonate, dimethyl (tert-butoxy) sulfonium hexafluoro antimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro antimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoro antimonate, dimethyl (fluorine methoxyl) sulfonium hexafluoro antimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoro antimonate, dimethyl (3-bromine propoxyl group) sulfonium hexafluoro antimonate, dimethyl (4-cyano group butoxy) sulfonium hexafluoro antimonate, dimethyl (8-nitro octyloxy) sulfonium hexafluoro antimonate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluoro antimonate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluoro antimonate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluoro antimonate, diphenyl iodine four (pentafluorophenyl group) borate, two (p-methylphenyl) iodine four (pentafluorophenyl group) borate, two (to tert-butyl-phenyl) iodine four (pentafluorophenyl group) borate, two (to octyl phenyl) iodine four (pentafluorophenyl group) borate, two (to octadecyl phenyl) iodine four (pentafluorophenyl group) borate, two (to octyloxyphenyl) iodine four (pentafluorophenyl group) borate, two (to octadecane oxygen base phenyl) iodine four (pentafluorophenyl group) borate, phenyl (to octadecane oxygen base phenyl) iodine four (pentafluorophenyl group) borate, (p-methylphenyl) (p-isopropyl phenyl) iodine four (pentafluorophenyl group) borate, methyl naphthalene iodide four (pentafluorophenyl group) borate, ethyl naphthalene iodide four (pentafluorophenyl group) borate, triphenylsulfonium four (pentafluorophenyl group) borate, three (p-methylphenyl) sulfonium four (pentafluorophenyl group) borate, three (p-isopropyl phenyl) sulfonium four (pentafluorophenyl group) borates, three (2,6-3,5-dimethylphenyl) sulfonium four (pentafluorophenyl group) borates, three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate, three (to cyano-phenyl) sulfonium four (pentafluorophenyl group) borate, three (rubigan) sulfonium four (pentafluorophenyl group) borate, dimethyl naphthyl sulfonium four (pentafluorophenyl group) borate, diethyl naphthyl sulfonium four (pentafluorophenyl group) borate, dimethyl (methoxyl) sulfonium four (pentafluorophenyl group) borate, dimethyl (ethoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (propoxyl group) sulfonium four (pentafluorophenyl group) borate, dimethyl (butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (octyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (octadecane oxygen base) sulfonium four (pentafluorophenyl group) borate, dimethyl (isopropoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (tert-butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (cyclopentyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (cyclohexyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (fluorine methoxyl) sulfonium four (pentafluorophenyl group) borate, dimethyl (2-chloroethoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (3-bromine propoxyl group) sulfonium four (pentafluorophenyl group) borate, dimethyl (4-cyano group butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (8-nitro octyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium four (pentafluorophenyl group) borate, dimethyl (2-hydroxyl isopropoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (three (trichloromethyl) methyl) sulfonium four (pentafluorophenyl group) borates etc., preferably enumerate two (p-methylphenyl) iodine hexafluorophosphates, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluorophosphate, two (to tert-butyl-phenyl) iodine hexafluorophosphate, triphenylsulfonium hexafluorophosphate, three (to tert-butyl-phenyl) sulfonium hexafluorophosphate, two (p-methylphenyl) iodine hexafluoro arsenate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro arsenate, two (to tert-butyl-phenyl) iodine hexafluoro arsenate, triphenylsulfonium hexafluoro arsenate, three (to tert-butyl-phenyl) sulfonium hexafluoro arsenate, two (p-methylphenyl) iodine hexafluoro antimonate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro antimonate, two (to tert-butyl-phenyl) iodine hexafluoro antimonate, triphenylsulfonium hexafluoro antimonate, three (to tert-butyl-phenyl) sulfonium hexafluoro antimonate, two (p-methylphenyl) iodine four (pentafluorophenyl group) borate, (p-methylphenyl) (p-isopropyl phenyl) iodine four (pentafluorophenyl group) borate, two (to tert-butyl-phenyl) iodine, triphenylsulfonium four (pentafluorophenyl group) borate, three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borates etc., more preferably enumerate two (p-methylphenyl) iodine hexafluoro antimonates, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro antimonate, two (to tert-butyl-phenyl) iodine hexafluoro antimonate, triphenylsulfonium hexafluoro antimonate, three (to tert-butyl-phenyl) sulfonium hexafluoro antimonate, two (p-methylphenyl) iodine four (pentafluorophenyl group) borate, (p-methylphenyl) (p-isopropyl phenyl) iodine four (pentafluorophenyl group) borate, two (to tert-butyl-phenyl) iodine four (pentafluorophenyl group) borate, triphenylsulfonium four (pentafluorophenyl group) borate, or three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate etc.
In addition, in the present invention, Photoepolymerizationinitiater initiater can also be used in combination light-initiated auxiliary agent.And if with Photoepolymerizationinitiater initiater and light-initiated auxiliary agent, because the sensitivity meeting of the photosensitive polymer combination that comprises these compositions further improves, the productive rate while using said composition to form sept also can improve, therefore preferred.
As light-initiated auxiliary agent, preferably use the compound shown in amines, carboxylic acid compound, multi-functional thiol's compound, following Chemical formula 13.
In light-initiated auxiliary agent, as the object lesson of amines, can enumerate: the fatty amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine; 4-dimethylaminobenzoic acid methyl esters, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid-2-Octyl Nitrite, benzoic acid-2-dimethylaminoethyl, N, N-dimethyl-p-toluidine, 4, the aromatic amines compounds such as 4 '-bis-(dimethylamino) benzophenone (common name: michaelis ketone), 4,4 '-bis-(diethylamino) benzophenone.As amines, preferably use aromatic amines compound.
As the object lesson of carboxylic acid compound, can enumerate the assorted acetic acid class of the aromatic series such as phenyl thioacetic acid, aminomethyl phenyl thioacetic acid, ethylphenyl thioacetic acid, Methylethyl phenyl thioacetic acid, 3,5-dimethylphenyl thioacetic acid, methoxyphenyl thioacetic acid, Dimethoxyphenyl thioacetic acid, chlorphenyl thioacetic acid, dichlorophenyl thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl glycocoll, naphthoxy acetic acid.
As the object lesson of multi-functional thiol's compound, can enumerate ethanthiol, the last of the ten Heavenly stems two mercaptan, 1, 4-dimethyl sulfydryl benzene, the two thiopropionates of butylene glycol, the two mercaptoacetates of butylene glycol, two mercaptoacetic acid glycol esters, trimethylolpropane tris mercaptoacetate, the two thiopropionates of butylene glycol, trimethylolpropane tris thiopropionate, trimethylolpropane tris mercaptoacetate, pentaerythrite tetrathio propionic ester, pentaerythrite four mercaptoacetates, trihydroxy ethyl three thiopropionates, pentaerythrite four (3-sulfydryl butyric ester), 1, two (3-sulfydryl butyryl acyloxy) butane of 4-etc.
The compound of Chemical formula 13 is as follows.
[chemistry 16]
(in above formula, the dotted line shown in X is the aromatic rings that the carbon number that can be replaced by halogen atom is 6～12;
Y is oxygen atom, sulphur atom;
R 1that carbon number is 1～6 alkyl;
R 2the carbon number that can be replaced by the halogen atom alkyl that is 1～12 or the aryl that can be replaced by halogen atom.〕
About the substituting group shown in above-mentioned Chemical formula 13 and the concrete example of compound, the disclosure that Korea S's publication 10-2008-0059048 communique is recorded is referenced in this manual.
Taking pressed powder as benchmark, be 100 weight portions with respect to the total amount of alkali soluble resin and photo-curable monomer, the content of Photoepolymerizationinitiater initiater of the present invention is generally 0.1～40 weight portion, be preferably 1～30 weight portion, taking above-mentioned as benchmark, the content of light-initiated auxiliary agent is generally 0.1～50 weight portion, is preferably 1～40 weight portion.If the use amount of Photoepolymerizationinitiater initiater is in above-mentioned scope, because the sensitivity meeting of photosensitive polymer combination improves, the intensity of sept and the flatness on sept surface that use said composition to form are all excellent, therefore preferred.In addition, if the use amount of light-initiated auxiliary agent, in above-mentioned scope, because the sensitivity meeting of photosensitive polymer combination further improves, is used the productive rate of the sept of said composition formation also can improve, therefore preferred.
< solvent >
Photosensitive polymer combination of the present invention, can use solvent used in the art and be not particularly limited.
, the ethylene glycol monoalkyl ether class such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether and ethylene glycol monobutyl ether as object lesson, can be used singly or in combination respectively two or more following solvents:, the diglycol dialkyl ethers such as diethylene glycol dimethyl ether, diethyl carbitol, diglycol ethyl methyl ether, diglycol dipropyl ether, diethylene glycol dibutyl ether, the ethylene glycol alkyl ether acetate esters such as methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, the aklylene glycol alkyl ether acetate esters such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, methoxy butyl acetate, acetic acid methoxyl pentyl ester, the propylene-glycol monoalky lether classes such as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, the propylene glycol dialkyl ethers such as Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether, the propylene glycol alkyl ether propionic acid esters such as propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propandiol butyl ether propionic ester, the butyl glycol monoalkyl ethers such as methoxybutanol, ethoxy butanols, propoxyl group butanols, butoxy butanols, the butylene glycol monoalky lether acetate esters such as methoxy butyl acetate, acetic acid ethoxy butyl ester, acetic acid propoxyl group butyl ester, acetic acid butoxy butyl ester, the butylene glycol monoalky lether propionic acid esters such as propionic acid methoxyl butyl ester, propionic acid ethoxy butyl ester, propionic acid propoxyl group butyl ester, propionic acid butoxy butyl ester, the dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol MEE, the arene such as benzene,toluene,xylene, sym-trimethyl benzene, the ketones such as butanone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, the alcohols such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid propyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxyl group methyl acetate, propoxyl group ethyl acetate, propoxyl group propyl acetate, propoxyl group butyl acetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, the ester classes such as 3-butoxy butyl propionate, the ring-type such as tetrahydrofuran, pyrans ethers, the cyclic ester classes such as gamma-butyrolacton etc.
In above-mentioned solvent, consider from the viewpoint of coating and drying property, preferably be set forth in boiling point in above-mentioned solvent and be the organic solvent of 100 DEG C～200 DEG C, more preferably enumerate aklylene glycol alkyl ether acetate esters, ketone, butylene glycol alkyl ether acetate esters, butylene glycol monoalkyl ethers, 3-ethoxyl ethyl propionate, the ester classes such as 3-methoxy methyl propionate, more preferably be used singly or in combination respectively two or more following solvents:, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxy butyl acetate, methoxybutanol, 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate etc.
With respect to the photosensitive polymer combination of 100 weight portions, the solvent in photosensitive polymer combination of the present invention is 60～90 weight portions, is preferably 70～85 weight portions.If solvent is in the scope of 60～90 weight portions, due to the coating excellence in the time that apparatus for coating such as using roll coater, spin coater, slit and rotary coating machine, slit coater (being sometimes also called mould coating machine (die coater)), ink-jet is coated with, therefore preferred.
< adjuvant >
Photosensitive polymer combination of the present invention, can also further optionally comprise the adjuvants such as filling agent, other macromolecular compounds, hardening agent, levelling agent, surfactant, closely sealed promoter, antioxidant, ultraviolet light absorber, anti-polycoagulant, chain-transferring agent.
As the object lesson of above-mentioned filling agent, can enumerate glass, silicon dioxide, aluminium oxide etc.
As the object lesson of above-mentioned other macromolecular compounds, can enumerate: the curable resins such as epoxy resin, maleimide resin; The thermoplastic resins such as polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, poly-fluoroalkyl acrylate, polyester, polyurethane etc.
Solidify and improve physical strength and use above-mentioned hardening agent for deep, as the object lesson of hardening agent, can enumerate epoxy compound, polyfunctional isocyanate's compound, melamine compound, oxetane compound etc.
In above-mentioned hardening agent, as the object lesson of epoxy compound, can enumerate bisphenol-A based epoxy resin, hydrogenated bisphenol A based epoxy resin, Bisphenol F based epoxy resin, A Hydrogenated Bisphenol A F based epoxy resin, phenol aldehyde type epoxy resin, other aromatic series based epoxy resin, alicyclic based epoxy resin, diglycidyl esters resin, diglycidyl amine resins, or the brominated derivative of above-mentioned epoxy resin, aliphatics except epoxy resin and brominated derivative thereof, alicyclic or aromatic epoxy compound, butadiene (being total to) polymer ring oxide, isoprene (being total to) polymer ring oxide, (methyl) glycidyl acrylate (being total to) polymkeric substance, triglycidyl group chlorinated isocyanurates etc.
In above-mentioned hardening agent, as the object lesson of oxetane compound, can enumerate the two oxetanes of carbonic ester, the two oxetanes of dimethylbenzene, the two oxetanes of hexane diacid, the two oxetanes of terephthalate, the two oxetanes of cyclohexane dicarboxylic acid etc.
About above-mentioned hardening agent, the curing auxiliary compounds that the oxetanes skeleton of epoxy radicals, oxetane compound that can make epoxy compound can be carried out to ring-opening polymerization is together with hardening agent and use.As above-mentioned curing auxiliary compounds, for example, can enumerate polybasic carboxylic acid class, polybasic acid anhydride class, acid-producing agent etc.
The commercially available product that above-mentioned carboxyanhydrides can be used as epoxy curing agent to sell.As above-mentioned epoxy curing agent, for example, can enumerate trade name ア デ カ ハ ー ド ナ ー EH-700 (Asahi Denka Co., Ltd.'s manufacture), trade name リ カ シ ッ De HH (New Japan Chem Co., Ltd's manufacture), trade name MH-700 (New Japan Chem Co., Ltd's manufacture) etc.It is two or more that the hardening agent of above-mentioned example can use separately or mix use.
As above-mentioned levelling agent, can use commercially available surfactant, for example can enumerate the surfactants such as silicon class, fluorine class, ester class, cationic, anionic species, nonionic class, both sexes class etc., these compositions can use separately respectively or be used in combination two or more.
As above-mentioned surfactant, for example, except polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyethylene glycol di class, sorbitan fatty acid esters class, fatty acid modified polyesters, tertiary amine modified polyurethane, outside polyethyleneimine: amine etc., can also enumerate trade name: KP (Shin-Etsu Chemial Co., Ltd's manufacture), Port リ フ ロ ー (Kyoeisha Chemical Co., Ltd.'s manufacture), エ Off ト ッ プ (manufacture of the ト ー ケ of Co., Ltd. system プ ロ ダ Network Star), メ ガ Off ァ ッ Network (Dainippon Ink. & Chemicals Inc's manufacture), Off ロ ラ ー De (manufacture of Sumitomo ス リ ー エ system Co., Ltd.), ア サ ヒ ガ ー De, サ ー Off ロ Application (more than, Co., Ltd. of Asahi Glass manufactures), ソ Le ス パ ー ス (manufacture of ゼ ネ カ Co., Ltd.), EFKA (manufacture of EFKACHEMICALS company), PB821 (Ajincomoto Co., Inc's manufacture) etc.
As above-mentioned closely sealed promoter, preferred silane compounds, specifically can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane etc.
As above-mentioned antioxidant, specifically can enumerate the 2-tert-butyl group-6-(the 3-tert-butyl group-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl acrylate, 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxyl group]-2,4,8,10-tetra-tert dibenzo [d, f] [1,3,2] dioxa phosphorus heterocycle heptene, two [2-{ 3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, the 1-dimethyl ethyls]-2,4,8 of 3,9-, 10-tetra-oxaspiros [5.5] undecane, 2,2 '-di-2-ethylhexylphosphine oxide (6-tert-butyl-4-methyl-Phenol), 4,4 '-butylidene two (the 6-tert-butyl group-3-methylphenol), 4,4 '-thiobis (the 2-tert-butyl group-5-methylphenol), 2,2 '-thiobis (6-tert-butyl-4-methyl-Phenol), dilauryl 3,3 '-thiodipropionate, myristyl 3,3 '-thiodipropionate, distearyl 3,3 '-thiodipropionate, pentaerythrite four (3-lauryl thiopropionate), 1,3,5-tri-(3,5-, bis--tertiary butyl-4-hydroxy benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones, 3,3 ', 3 ', 5,5 ', 5 ' '-six-tert-butyl group-a, a ', a ' '-(sym-trimethyl benzene-2,4,6-, tri-bases) three paracresol, pentaerythrite four [3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester], BHT etc.
As above-mentioned ultraviolet light absorber, specifically can enumerate: 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, alkoxy benzophenone etc.
As above-mentioned anti-polycoagulant, specifically can enumerate sodium polyacrylate etc.
As above-mentioned chain-transferring agent, specifically can enumerate lauryl mercaptan, 2,4-diphenyl-4-methyl-1-pentene etc.
< sept and image display device >
The invention provides a kind of sept and comprise the image display device of this sept, described sept after photosensitive polymer combination has been formed to predetermined pattern, expose and develop and form.Described device used for image display sept is for example by carrying out photocuring and development after photosensitive resin coating composition on base material, and forms pattern and prepare.
First, upper at substrate (normally glass) or the preformed layer being made up of the pressed powder of photosensitive polymer combination, photosensitive resin coating composition, carries out heat drying afterwards, thereby remove the volatile ingredients such as solvent, and obtain level and smooth film.
As coating process, for example, be coated with by spin-coating method, curtain coating rubbing method, rolling method, slit and method of spin coating or slot coated method etc.After coating, carry out heat drying (prebake) or heat after drying under reduced pressure, making the volatile ingredient volatilizations such as solvent.Here, heating-up temperature is generally 70～200 DEG C, is preferably 80～130 DEG C.Coating thickness after heat drying is generally 1～8 μ m left and right.For the film of above-mentioned gained, via being used to form the mask of expected pattern and irradiation ultraviolet radiation., irradiate equably parallel rays for exposure portion entirety here, in addition, preferably use the device such as mask aligner or steeper, thereby the tram of mask and substrate is matched.If irradiation ultraviolet radiation, being irradiated to ultraviolet part can solidify.
Above-mentioned ultraviolet ray can be used g line (wavelength: 436nm), h line, i line (wavelength: 365nm) etc.Ultraviolet irradiation amount can suitably be selected as required, is not subject to restriction of the present invention.If the film solidifying after finishing is contacted with developer solution, make non-exposed portion dissolve and develop, just can obtain the sept with target pattern shape.
Above-mentioned developing method can be any method in solution additive process, infusion process, spray-on process etc.In addition, in the time developing, can make substrate with arbitrarily angled inclination.Above-mentioned developer solution normally comprises the aqueous solution of alkali compounds and surfactant.Above-mentioned alkali compounds can be any in inorganic and organic basic compound.As the object lesson of inorganic alkaline compound, can enumerate NaOH, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium borate, potassium borate, ammonia etc.In addition, as the object lesson of organic basic compound, can enumerate Tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, MMA, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single isopropylamine, diisopropylamine, monoethanolamine etc.These inorganic and organic basic compounds can use separately respectively or be used in combination two or more.The concentration of the alkali compounds in alkaline-based developer is preferably 0.01～10 quality %, more preferably 0.03～5 quality %.
Surfactant in above-mentioned alkaline-based developer can use at least one being selected from nonionic class surfactant, anionic species surfactant or cationic surfactant.
As the object lesson of above-mentioned nonionic class surfactant, can enumerate polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene deriv, ethylene oxide/propylene oxide segmented copolymer, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine etc.
As the object lesson of above-mentioned anionic species surfactant, can enumerate: the higher alcohol sulfuric ester salts such as lauryl alcohol sodium sulfovinate or oleyl alcohol sodium sulfovinate; The alkylsurfuric acid such as lauryl sodium sulfate or ammonium lauryl sulfate salt; The alkyl aryl sulfonate classes such as neopelex or dodecyl sodium naphthalene sulfonate etc.
As the object lesson of above-mentioned cationic surfactant, can enumerate amine salt or the quaternary ammonium salts etc. such as octadecyl amine hydrochlorate or DTAC.These surfactants can use separately respectively or be used in combination two or more.
The concentration of the surfactant in above-mentioned developer solution is generally 0.01～10 quality %, is preferably 0.05～8 quality %, more preferably 0.1～5 quality %.After development, wash, can also at 150～230 DEG C, carry out as required 10～60 minutes after cure.
Use photosensitive polymer combination of the present invention, by above-mentioned each operation, on substrate or on colored filter substrate, can form pattern.Above-mentioned pattern is of great use as the light spacer for image display device (photospacer).
The T/B of the sept being formed by photosensitive polymer combination of the present invention is than excellent.T/B ratio refers to, the value that the upper diameter in spacer patterns is obtained divided by lower diameter.In the present invention, the top of pattern uses 95% the surface level with respect to the whole height of pattern and from basal surface to whole height to define, and the bottom of pattern uses 5% the surface level with respect to the whole height of pattern and from basal surface to whole height to define.
T/B ratio is the bigger the better, and the T/B ratio of sept of the present invention is 40～100%, is preferably 50～90%.
As mentioned above, sept of the present invention can be effectively for image display devices such as liquid crystal indicators, the sensitivity excellence of sept of the present invention, even if exposure is low, its cross-linking density is also high, with the adaptation excellence of substrate, and there is high resiliency response rate and be out of shape less physical strength because external pressure causes.
Below, in order easily to understand the present invention, provide preferred embodiment, but these embodiment just illustrate the present invention, and can not limit the scope of incidental claim, in the scope of category of the present invention and technological thought, can embodiment be carried out numerous variations and be revised, this is very clear and definite to those skilled in the art, and these changes and correction also belong to the scope of incidental claim certainly.
[synthesis example: alkali soluble resin (A-1)]
In the 1L flask that possesses reflux condenser, tap funnel and stirrer, flow velocity with 0.02L/ minute passes into nitrogen, under nitrogen environment, add 200 mass parts 3-methoxyl-n-butyl alcohols and 105 mass parts 3-methoxyl butylacetic acid esters, be heated to while stirring 70 DEG C.Then, be dissolved in potpourri (mol ratio 50:50), 60 mass parts methacrylic acids and the 140 mass parts 3-methoxyl butylacetic acid esters of the following Chemical formula 28 of 240 mass parts and Chemical formula 29, prepared solution.
[chemistry 17]
[chemistry 18]
Use tap funnel, with 4 hours, the lysate of having prepared is splashed into insulation in the flask of 70 DEG C.On the other hand, by the polymerization initiator of 30 mass parts 2,2 '-azo two (2,4-methyl pentane nitrile) is dissolved in 225 mass parts 3-methoxyl butylacetic acid esters makes solution, uses another tap funnel with 4 hours, this solution to be splashed in flask.After the solution dropping of polymerization initiator finishes, maintain 70 DEG C and be issued to 4 hours, being cooled to afterwards room temperature, is that 32.6 quality %, acid number are the solution of the multipolymer (Resin A-1) of 110mg-KOH/g (pressed powder conversion) thereby obtain pressed powder.
The weight-average molecular weight (Mw) of Resin A-1 obtaining is 13400, and molecular weight distribution is 2.50.
About the weight-average molecular weight (Mw) of above-mentioned multipolymer and the mensuration of number-average molecular weight (Mn), utilize under the following conditions GPC method to carry out.
Device: HLC-8120GPC (TOSOH Co., Ltd's manufacture);
Post: TSK-GELG4000HXL+TSK-GELG2000HXL (series connection);
Column temperature: 40 DEG C;
Mobile phase solvent: tetrahydrofuran;
Flow velocity: 1.0mL/ minute;
Injection rate IR: 50 μ L;
Detecting device: RI;
Working sample concentration: 0.6 quality % (solvent: tetrahydrofuran);
Correction standard substance: TSK polystyrene standard F-40, F-4, F-1, A-2500, A-500 (TOSOH Co., Ltd's manufacture).
Be compared to molecular weight distribution (Mw/Mn) with weight-average molecular weight obtained above and number-average molecular weight.
[embodiment 1～5 and comparative example 1～3]
The composition of recording according to following table 1 and composition, prepared photosensitive polymer combination (unit is weight portion).[table 1]
[test example]
< pattern forms >
Having cleaned successively the length of side with neutral detergent, water and alcohol is that the glass substrate (イ ー グ Le 2000, コ ー ニ Application グ companies of 2 inches manufacture), be dried afterwards.On this glass substrate with 100mJ/cm 2exposure (405nm) photosensitive polymer combination is exposed, carry out afterwards spin coating so that development, the flow of water and after thickness while curing reach 3.0 μ m, then prebake 3 minutes in cleaning oven, at 90 DEG C.After cooling, make to be coated with the substrate of photosensitive polymer combination and the interval of quartz glass photomask processed reaches 10 μ m, use exposure machine (TME-150RSK, ト ッ プ コ Application Co., Ltd. manufacture), under atmospheric environment, carry out irradiation with 100mJ/ exposure (405nm benchmark).In addition, about the irradiation that photosensitive polymer combination is carried out now, used the radiating light from extra-high-pressure mercury vapour lamp has been passed through to optical filter (LU0400, rising sun light splitting Co., Ltd. manufacture), and cut down into the light below 400nm.
In addition, as photomask, used the photomask that is formed with at grade following pattern.
(1) there is the foursquare transmittance section (pattern) that the length of side is 10 μ m, these foursquare 100 μ m that are spaced apart.
(2) there is the foursquare transmittance section (pattern) that the length of side is 15 μ m, these foursquare 100 μ m that are spaced apart.
After irradiation, for this substrate, above-mentioned film at 25 DEG C, soak 100 seconds to develop in the water class developer solution that containing 0.12% nonionic class surfactant and 0.04% potassium hydroxide, then after washing, is cured 20 minutes after in baking oven, at 220 DEG C.Place cooling after, use determining film thickness device (DEKTAK3, ULVAC Corp manufacture) to measure the thickness of the cured film of gained, its thickness is 3.0 μ m.
< transmitance >
Use microscope light splitting light measurer (OSP-SP200, Olympus Corp manufacture), measured the cured film of above-mentioned gained at the transmitance of 400nm (%).Transmitance when transmitance is converted into thickness and is 3.0 μ m, transmitance as described in Table 2.Preferably transmitance is close to 100%.
< live width, cross sectional shape >
Use scanning electron microscope (S-4200, Hitachi Co., Ltd manufacture), measured the live width of the cured film of above-mentioned gained, evaluated as follows cross sectional shape.Taking pattern with respect to the angle of substrate be less than 90 while spending as positive taper, taking angle as 90 degree when above as back taper, judge cross sectional shape.
If positive taper is owing to being difficult to occur the broken string of ITO wiring in the time forming display device, therefore preferred.
< mechanical property (full addendum modification and response rate) >
Use dynamically super micro-hardness tester (DUH-W201, Shimadzu Scisakusho Ltd manufacture), under following condition determination, (m) (μ m) with elasticity addendum modification for μ to measure the full addendum modification of the cured film of above-mentioned gained, and use measured value, calculate as follows response rate (%).If full addendum modification is few and response rate is large, be judged as this cured film hard.
Response rate (%)=[elasticity addendum modification (μ is m)]/[full addendum modification (μ is m)] × 100
Condition determination:
(a) test model: load-unloading test;
(b) test force: 5gf[SI unit conversion value: 49.0mN];
(c) loading speed: 0.45gf/sec[SI unit conversion value: 4.41mN/ second];
(d) retention time: 5 seconds;
(e) piston: cylindrical piston (diameter be 50 μ m).
< sensitivity >
About sensitivity, by 1000 photomasks that to have respectively diameter (size) be 5 μ m～20 μ m, be spaced apart the circular pattern of 1 μ m, do not come off and the size of 100% photomask when residual with the pattern that microscope evaluation has formed 3 μ m thickness.The size of photomask is less, and sensitivity is more excellent.
< T/B is than measuring >
Use above-mentioned composition, have in sputter on the glass substrate of ITO and form after pattern, the 3 d shape testing instrument SIS-2000 that utilizes SNUPrecision company to manufacture observes, basal surface from pattern is defined as to bottom CD (a), will 95% be defined as top CD (b) from basal surface to whole height to 5% of whole height, by the length of (b) divided by being multiplied by 100 and the value (=b/a × 100) that obtains is defined as T/B ratio after the length of (a).
[table 2]
In above-mentioned table 2, can confirm following situation: compared with comparative example 1～3, even if embodiments of the invention 1～6 exposure is low, also good with adaptation and the pattern form of substrate, elastic recovery rate excellence, not only there is the mechanical property that full addendum modification is few, and sensitivity excellence, particularly T/B ratio is improved.
In addition, can also confirm following situation: compared with embodiments of the invention, used the T/B of the comparative example 3 of two benzophenone class hydrogen donors to decline than remarkable.

Claims (10)

1. a photosensitive polymer combination, comprises alkali soluble resin, photo-curable monomer, Photoepolymerizationinitiater initiater, aminoacetophenone class or amino benzaldehyde hydrogen donor and solvent.
2. photosensitive polymer combination according to claim 1, wherein, described aminoacetophenone class or amino benzaldehyde hydrogen donor are the compounds shown in following Chemical formula 1:
[chemistry 1]
In above formula, R 1and R 2independent is respectively the alkyl of the straight or branched of carbon number 1～6, R 3that hydrogen, hydroxyl or carbon number are the alkyl of 1～10 straight or branched.
3. photosensitive polymer combination according to claim 1, wherein, described aminoacetophenone class hydrogen donor is to dimethylamino acetophenone.
4. photosensitive polymer combination according to claim 1, wherein, with respect to the composition of 100 weight portions, the described aminoacetophenone class or the amino benzaldehyde hydrogen donor that contain 0.1～20 weight portion.
5. photosensitive polymer combination according to claim 1, wherein, described Photoepolymerizationinitiater initiater comprises at least one Photoepolymerizationinitiater initiater being selected from acetophenones, bisglyoxaline class and oximes.
6. photosensitive polymer combination according to claim 5, wherein, described acetophenones Photoepolymerizationinitiater initiater is to be selected from diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzil dimethyl ketal, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-(2-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-Ethylbenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-propyl group benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-butyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2,3-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2,4-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methyl-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(the bromo-4-methoxy-benzyl of 2-)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer of propane-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-propyl group-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-butyl-2-amino (4-morpholino phenyl) ethane-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) propane-1-ketone, 2-methyl-2-amino (4-morpholino phenyl) butane-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) propane-1-ketone, 2-ethyl-2-amino (4-morpholino phenyl) butane-1-ketone, 2-methyl-2-methylamino (4-morpholino phenyl) propane-1-ketone, 2-methyl-2-dimethylamino (4-morpholino phenyl) propane-1-ketone, at least one in 2-methyl-2-diethylamino (4-morpholino phenyl) propane-1-ketone.
7. photosensitive polymer combination according to claim 5, wherein, described bisglyoxaline class Photoepolymerizationinitiater initiater is to be selected from 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2, 3-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(alkoxyl phenyl) bisglyoxaline, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(dialkoxy phenyl) bisglyoxaline, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetra-(tri-alkoxy phenyl) bisglyoxalines and 4, 4 ', 5, at least one in the imidazolium compounds that the phenyl of 5 ' is replaced by alkoxy carbonyl group.
8. photosensitive polymer combination according to claim 5, wherein, described oximes Photoepolymerizationinitiater initiater is to be selected from least one in compound shown in compound shown in O-carbethoxyl group-α-oximido-1-phenyl-propane-1-ketone, following chemical formula 5 and following chemical formula 6:
[chemistry 2]
[chemistry 3]
9. a sept, it is to be formed by the photosensitive polymer combination described in any one in claim 1 to 8.
10. an image display device, it comprises sept claimed in claim 9.
CN201410086476.1A 2013-03-08 2014-03-10 Photosensitive Resin Composition And Spacer Preprared From The Same Pending CN104035278A (en)

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